JPWO2003014421A1 - Method for producing high-purity nickel, high-purity nickel, sputtering target comprising the same, and thin film formed by the sputtering target - Google Patents

Method for producing high-purity nickel, high-purity nickel, sputtering target comprising the same, and thin film formed by the sputtering target Download PDF

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JPWO2003014421A1
JPWO2003014421A1 JP2003519547A JP2003519547A JPWO2003014421A1 JP WO2003014421 A1 JPWO2003014421 A1 JP WO2003014421A1 JP 2003519547 A JP2003519547 A JP 2003519547A JP 2003519547 A JP2003519547 A JP 2003519547A JP WO2003014421 A1 JPWO2003014421 A1 JP WO2003014421A1
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nickel
anolyte
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JP3876253B2 (en
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新藤　裕一朗
裕一朗 新藤
竹本　幸一
幸一 竹本
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Nippon Mining Holdings Inc
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals

Abstract

電解液としてニッケル含有溶液を用いて電解する際に、アノライトをｐＨ２〜５に調整し、アノライトに含有されている鉄、コバルト、銅等の不純物を、酸化剤を入れて該不純物を水酸化物として沈殿除去するか、若しくは予備電解により該不純物を除去するか、又はＮｉ箔を入れて置換反応により該不純物を除去するかの、いずれか１又は２以上の方法を組合せることにより不純物を除去した後、さらにフィルターを使用して不純物を除去し、除去後の液をカソライトとして使用し電解する。不純物が多く含有されるニッケル原料から、ニッケル含有溶液を用いて電解精製する簡便な方法に関し、純度５Ｎ（９９．９９９ｗｔ％）以上の高純度ニッケルを効率的に製造する技術を提供する。When electrolysis is performed using a nickel-containing solution as an electrolytic solution, the anolyte is adjusted to pH 2 to 5, and impurities such as iron, cobalt, and copper contained in the anolyte are added with an oxidizing agent to convert the impurities to hydroxide. The impurities are removed by a combination of one or more of the following methods: removing the impurities by precipitation, removing the impurities by preliminary electrolysis, or removing the impurities by a substitution reaction with a Ni foil. After that, impurities are further removed using a filter, and the solution after the removal is used as catholyte for electrolysis. Provided is a technique for efficiently producing high-purity nickel having a purity of 5N (99.999 wt%) or more with respect to a simple method for electrolytically refining a nickel raw material containing many impurities using a nickel-containing solution.

Description

技術分野
この発明は、ニッケル含有溶液を用いて電解精製により純度５Ｎ（９９．９９９ｗｔ％）以上の高純度ニッケルを製造する方法、高純度ニッケル、同高純度ニッケルからなるスパッタリングターゲット及び該スパッタリングターゲットにより形成した薄膜に関する。
背景技術
一般に、高純度ニッケルは、アルカリ金属、放射性元素、遷移金属元素、ガス成分を極力減少させることが要求されており、ＶＬＳＩの電極及び配線の形成、あるいは磁性薄膜を形成するための、特にスパッタリングターゲット材として広範囲に使用されている。
Ｎａ、Ｋ等のアルカリ金属はゲート絶縁膜中を容易に移動し、ＭＯＳ−ＬＳＩ界面特性の劣化原因となる。Ｕ，Ｔｈ等の放射性元素は、放出するα線によって素子のソフトエラーの原因となる。一方、Ｆｅ等の遷移金属元素も界面接合部のトラブルの原因となる。
さらに、炭素、酸素などのガス成分も、スパッタリングの際のパーティクル発生原因となるため好ましくない。
一般に、５Ｎレベルの高純度ニッケルを製造する場合には、イオン交換や溶媒抽出等で溶液を精製し、これをさらに電解採取又は電解精製によって高純度化を行うことが普通であるが、このような溶媒抽出工程をとる方法は工程が複雑であり、また特殊な溶媒を必要とすることから抽出剤の安全を考慮する必要があるなど、効率的でないという問題があった。
５Ｎレベルの高純度ニッケルを製造する場合に、ニッケル含有溶液を用いて電解により製造するのが比較的簡単な方法と考えられるが、上記のような溶媒抽出等の工程を経るものは、必ずしも効率的とは言えなかった。
発明の開示
本発明は、鉄、炭素、酸素等が多く含有されるニッケル原料から、ニッケル含有溶液を用いて電解する簡便な方法を提供するものであり、同原料から純度５Ｎ（９９．９９９ｗｔ％）以上の高純度ニッケルを効率的に製造する技術を提供することを目的としたものである。
上記問題点を解決するため、ニッケル含有溶液のアノライトから鉄等の不純物を水酸化物として除去し、除去後の液をカソライトとして使用することにより、能率良く高純度ニッケルを製造できるとの知見を得た。
この知見に基づき、本発明は
１．電解液としてニッケル含有溶液を用いて電解する際に、アノライトをｐＨ２〜５に調整し、アノライトに含有されている鉄、コバルト、銅等の不純物を、酸化剤を入れて該不純物を水酸化物として沈殿除去するか、若しくは予備電解により該不純物を除去するか、又はＮｉ箔を入れて置換反応により該不純物を除去するかの、いずれか１又は２以上の方法を組合せることにより不純物を除去した後、さらにフィルターを使用して不純物を除去し、除去後の液をカソライトとして使用し電解することを特徴とする高純度ニッケルの製造方法
２．アノードとカソードを隔膜で仕切り、アノライトを間歇的又は連続的に抜き出し、これに酸化剤を入れて鉄等の不純物を水酸化物として沈殿させた後、さらにフィルターを使用して不純物を除去し、除去後の液をカソード側に間歇的又は連続的に入れることを特徴とする上記１記載の高純度ニッケルの製造方法
３．アノードとカソードを隔膜で仕切り、アノライトを間歇的又は連続的に抜き出し、このアノライトを予備電解して鉄、コバルト、銅等の不純物を除去した後、さらにフィルターを使用して不純物を除去し、除去後の液をカソード側に間歇的又は連続的に入れることを特徴とする上記第１記載の高純度ニッケルの製造方法。
４．アノードとカソードを隔膜で仕切り、アノライトを間歇的又は連続的に抜き出し、このアノライトにニッケル箔を入れて置換反応により、鉄、コバルト、銅等の不純物を除去した後、さらにフィルターを使用して不純物を除去し、除去後の液をカソード側に間歇的又は連続的に入れることを特徴とする上記１記載の高純度ニッケルの製造方法。
５．フィルターとして活性炭を使用することを特徴とする上記１〜４のそれぞれに記載の高純度ニッケルの製造方法
６．フィルター通過後の、電解液中の鉄の濃度が１ｍｇ／Ｌ以下であることを特徴とする上記１〜５のそれぞれに記載の高純度ニッケルの製造方法
７．電解によって得られた電析ニッケルを電子ビーム溶解等の真空溶解を行うことを特徴とする上記１〜６のそれぞれに記載の高純度ニッケルの製造方法
８．ガス成分を除き５Ｎ（９９．９９９ｗｔ％）以上であり、不純物としてＯ：３０ｗｔｐｐｍ以下、Ｃ，Ｎ，Ｓ，Ｐ，Ｆがそれぞれ１０ｗｔｐｐｍ以下であることを特徴とする高純度ニッケル、同高純度ニッケルからなるターゲット及び同ターゲットを使用してスパッタリングにより形成した薄膜
９．上記１〜７により製造したガス成分を除き５Ｎ（９９．９９９ｗｔ％）以上であり、不純物としてＯ：３０ｗｔｐｐｍ以下、Ｃ，Ｎ，Ｓ，Ｐ，Ｆがそれぞれ１０ｗｔｐｐｍ以下であることを特徴とする高純度ニッケル、同高純度ニッケルからなるターゲット及び同ターゲットを使用してスパッタリングにより形成した薄膜
を提供するものである。
発明の実施の形態
図１に示す電解槽１を用い、４Ｎレベルの塊状のニッケル原料２をアノードバスケット３に入れてアノード５とし、カソード４にニッケル等を使用して電解を行う。ニッケル原料には、主として鉄、炭素、酸素等が多く含有されている。
電解に際しては、浴温１０〜７０°Ｃ、ニッケル濃度２０〜１２０ｇ／Ｌ、電流密度０．１〜１０Ａ／ｄｍ２で実施する。電流密度０．１Ａ／ｄｍ２未満では生産性が悪く、また１０Ａ／ｄｍ２を超えるとノジュールが発生してしまい、アノード５とカソード４が接触するため好ましくないので、電流密度は０．１〜１０Ａ／ｄｍ２の範囲とする。
前記アノード５とカソード４は隔膜６で仕切り、アノライトを間歇的又は連続的に抜き出す。アノライトはｐＨ２〜５に調整されている。カソードボックスは、隔膜を介して外側の液（アノライト）と分離している。抜き出したアノライトに酸化剤７を入れて鉄、コバルト、銅等の不純物を水酸化物として沈殿させる。すなわち、２価の鉄が酸化剤７により３価となりＦｅ（ＯＨ）３として沈殿する。酸化剤７としては過酸化水素、硝酸等が使用できる。
また、抜き出したアノライトを予備電解槽に入れ、電解により鉄、コバルト、銅等の不純物を除去することができる。
さらにまた、抜き出したアノライトを置換槽に入れ、ニッケル箔を使用して電解液中の鉄、コバルト、銅等の不純物との置換を行いこれらの不純物を除去することができる。
図１は、酸化剤を入れる工程を示しているが、この工程７を予備電解又は置換方法の置き換えることにより、容易に除去できる。
上記の酸化剤、予備電解又は置換方法のそれぞれを組合せて該不純物を除去することもできる。
この沈殿物等の不純物を、フィルター８を使用して除去する。フィルターには、活性炭を使用するのが良い。活性炭のフィルター８は前記沈殿した酸化物等の不純物以外に、容器等から溶出する有機物を除去する効果もある。以上によって、電解液中の鉄の濃度を１ｍｇ／Ｌ以下とすることができる。
不純物の除去後、この液をカソード側に間歇的又は連続的に導入し、カソライトとして使用して電解精製する。
電流効率は８０〜１００％となる。以上によって、純度５Ｎの電析ニッケル（カソードに析出）が得られる。すなわち、ガス成分を除き５Ｎ（９９．９９９ｗｔ％）以上であり、不純物としてＯ：３０ｗｔｐｐｍ以下、Ｃ，Ｎ，Ｓ，Ｐ，Ｆ，Ｈをそれぞれ１０ｗｔｐｐｍ以下とすることができる。
さらに、電解によって得られた電析ニッケルを電子ビーム溶解等の真空溶解を行うことができる。この真空溶解によって、Ｎａ、Ｋ等のアルカリ金属やその他の揮発性不純物及びガス成分を効果的に除去できる。
また、本発明においては、イオン交換樹脂や溶媒抽出を行っていないので、有機物が混入することがなく、有機溶媒に起因する不純物元素を抑制できる。
実施例及び比較例
次に、本発明の実施例について説明する。なお、本実施例はあくまで一例であり、この例に制限されるものではない。すなわち、本発明の技術思想の範囲内で、実施例以外の態様あるいは変形を全て包含するものである。
（実施例１）
図１に示すような電解槽を用い、４Ｎレベルの塊状のニッケル原料１ｋｇをアノードとし、カソードに２Ｎレベルのニッケル板を使用して電解を行った。原料の不純物の含有量を表１に示す。ニッケル原料には、主として鉄、炭素、酸素等が多く含有されている。
浴温５０°Ｃ、硫酸系電解液で弗酸を１ｍｏｌ／Ｌを添加し、ニッケル濃度５０ｇ／Ｌ、電流密度２Ａ／ｄｍ２、電解時間４０ｈｒ実施した。
液のｐＨを２に調節した。この時、アノライトを間歇的に抜き出す。抜き出したアノライトに過酸化水素（Ｈ２Ｏ２）を入れて、２価の鉄を３価に変え、鉄等の不純物を水酸化物Ｆｅ（ＯＨ）３として沈殿させた。
さらに、この沈殿物等の不純物を、活性炭フィルターを使用して除去した。以上によって、電解液中の鉄の濃度が１ｍｇ／Ｌ以下とすることができた。
不純物の除去後、この液をカソード側すなわちアノードバスケット内に間歇的に導入し、カソライトとして使用して電解した。
電析ニッケル（カソードに析出）約１ｋｇを得た。純度は５Ｎを達成した。すなわち、ガス成分を除き５Ｎ（９９．９９９ｗｔ％）以上であり、不純物としてＯ：３０ｗｔｐｐｍ以下、Ｃ，Ｎ，Ｓ，Ｐ，Ｆがそれぞれ１０ｗｔｐｐｍ以下とすることができた。以上の結果を原料と対比して、表１に示す。

Figure 2003014421
（実施例２）
実施例１と同じ電解槽を用い、４Ｎレベルの塊状の原料ニッケルをアノードとし、カソードに３Ｎレベルのニッケル板を使用して電解を行った。
浴温３０°Ｃ、塩酸系電解液で、ニッケル濃度８０ｇ／Ｌ、電流密度５Ａ／ｄｍ２、電解時間４０ｈｒ実施した。
実施例１と同様に、液のｐＨを２に調節した。この時、アノライトを間歇的に抜き出す。抜き出したアノライトに過酸化水素（Ｈ２Ｏ２）を入れて、２価の鉄を３価に変え、鉄等の不純物を水酸化物Ｆｅ（ＯＨ）３として沈殿させた。
さらに、この沈殿物等の不純物を、活性炭フィルターを使用して除去した。以上によって、電解液中の鉄の濃度が１ｍｇ／Ｌ以下とすることができた。
不純物の除去後、この液をカソード側すなわちアノードバスケット内に間歇的に導入し、カソライトとして使用して電解した。
電析ニッケル（カソードに析出）約１ｋｇを得た。この電析ニッケルをさらに電子ビーム溶解した。電子ビーム溶解条件は、１Ａ、３０ｋＷ、真空度２〜５×１０−４ｍｍＨｇで実施した。以上の結果を、同様に表１に示す。
（比較例１）
図１に示すような電解槽を用い、４Ｎレベルの塊状のニッケル原料１ｋｇをアノードとし、カソードに３Ｎレベルのニッケル板を使用して電解を行った。原料の不純物の含有量を表１に示す。
浴温５０°Ｃ、硫酸系電解液で弗酸を１ｍｏｌ／Ｌを添加し、ニッケル濃度５０ｇ／Ｌ、電流密度２Ａ／ｄｍ２、電解時間４０ｈｒ実施した。
液のｐＨを２は調節した。この時、アノライトを抜き出さず、そのまま電解を続けた。
電析ニッケル（カソードに析出）約１ｋｇを得た。
以上の結果を、同様に表１に示す。
表１に示すように、実施例１では、原料の鉄５０ｗｔｐｐｍが２ｗｔｐｐｍに、酸素２００ｗｔｐｐｍが２０ｗｔｐｐｍに、炭素５０ｗｔｐｐｍが１０ｗｔｐｐｍ未満、Ｃ，Ｎ，Ｓ，Ｐ，Ｆ１０ｗｔｐｐｍをそれぞれ１０ｗｔｐｐｍ未満とすることができた。
また、実施例２では、鉄１ｗｔｐｐｍ、酸素１０ｗｔｐｐｍ未満、その他の不純物１０ｗｔｐｐｍ未満とすることができた。
これに対し、比較例１では、Ｃ，Ｎ，Ｓ，Ｐ，Ｆ１０ｗｔｐｐｍをそれぞれ１０ｗｔｐｐｍ未満とすることができたが、鉄５０ｗｔｐｐｍ、また酸素６０ｗｔｐｐｍで実施例に比べ精製効果が劣り、特に鉄の除去が困難であった。
（実施例３）
３Ｎレベルの塊状のニッケル原料１ｋｇをアノードとし、カソードに２Ｎレベルのアルミニウム板を使用して電解を行った。原料の不純物の含有量を表２に示す。このニッケル原料には、鉄、コバルト、銅、炭素、酸素等が多く含有されている。
電解条件は、浴温４０°Ｃ、硫酸系電解液に塩酸を１ｍｏｌ／Ｌを添加し、ニッケル濃度１００ｇ／Ｌ、電流密度３Ａ／ｄｍ２、電解時間２５ｈｒ実施した。
液のｐＨは２．５に調節した。この時、アノライトを間歇的に抜き出す。抜き出したアノライトは、予備電解槽で電流密度０．１Ａ／ｄｍ２で電解を行い、鉄、コバルト、銅等を除去した。
さらに、活性炭フィルターを使用して電解液中の有機物を除去した。以上によって、電解液中の鉄、コバルト、銅等の濃度を１ｍｇ／Ｌ以下にすることができた。
不純物の除去後、この液をカソード側すなわちアノードバスケット内に間歇的に導入し、カソライトとして使用して電解した。
その結果、電析ニッケル約１．１ｋｇを得た。純度は５Ｎを達成した。すなわち、ガス成分を除き５Ｎ以上であり、不純物としてＯ：２０ｗｔｐｐｍ、Ｃ，Ｎ，Ｓ，Ｐ，Ｆはそれぞれ１０ｗｔｐｐｍ以下とすることができた。以上の結果を原料と対比して、表２に示す。
（実施例４）
３Ｎレベルの塊状のニッケル原料１ｋｇをアノードとし、カソードに２Ｎレベルのチタン板を使用して電解を行った。原料の不純物の含有量を表２に示す。このニッケル原料には、鉄、コバルト、銅、炭素、酸素等が多く含有されている。
電解条件は、浴温６０°Ｃ、硫酸系電解液に塩酸を１ｍｏｌ／Ｌを添加し、ニッケル濃度１００ｇ／Ｌ、電流密度１．５Ａ／ｄｍ２、電解時間５０ｈｒ実施した。
液のｐＨは２．７に調節した。この時、アノライトを間歇的に抜き出す。抜き出したアノライトは、置換槽で２ＮレベルのＮｉ箔で電解液中の不純物との置換を行い、鉄、コバルト、銅等を除去した。
さらに、活性炭フィルターを使用して電解液中の有機物を除去した。以上によって、電解液中の鉄、コバルト、銅等の濃度を１ｍｇ／Ｌ以下にすることができた。
不純物の除去後、この液をカソード側すなわちアノードバスケット内に間歇的に導入し、カソライトとして使用して電解した。
その結果、電析ニッケル約１．１ｋｇを得た。純度は５Ｎを達成した。すなわち、ガス成分を除き５Ｎ以上であり、不純物としてＯ：２０ｗｔｐｐｍ、Ｃ，Ｎ，Ｓ，Ｐ，Ｆはそれぞれ１０ｗｔｐｐｍ以下とすることができた。以上の結果を原料と対比して、同様に表２に示す。
（実施例５）
上記実施例３の工程において、アノライトを間歇的に抜き出し、抜き出したアノライトを予備電解槽で電流密度０．１Ａ／ｄｍ２で電解を行い、これをさらに実施例４の置換槽における置換反応と同一の条件で鉄、コバルト、銅等の不純物を除去した（予備電解と置換反応の組合せ）。
そして、この工程以外は実施例３と同一の工程により電析ニッケル約１．１ｋｇを得た。この結果、純度はガス成分を除き５Ｎ以上であり、不純物としてＯ：１０ｗｔｐｐｍ、Ｃ，Ｎ，Ｓ，Ｐ，Ｆはそれぞれ１０ｗｔｐｐｍ以下とすることができた。以上の結果を原料と対比して、同様に表２に示す。
Figure 2003014421
以上から、本発明の、アノードとカソードを隔膜で仕切り、該アノライトを間歇的又は連続的に抜き出し、これに酸化剤を入れて鉄等の不純物を水酸化物として沈殿させ、さらにフィルターを使用して不純物を除去し、除去後の液をカソード側に間歇的又は連続的に入れて電解することは、鉄を効果的に除去し、高純度ニッケルを得る上で、簡便な方法でありかつ極めて有効であることが分かる。
発明の効果
以上に示すように、電解液としてニッケル含有溶液を用い、鉄、炭素、酸素等が多く含有されるニッケル原料から、ニッケル含有溶液を用いて電解精製する簡便な方法を提供するものであり、簡単な製造工程の改良により、同原料から純度５Ｎ（９９．９９９ｗｔ％）以上の高純度ニッケルを効率的に製造できるという著しい効果を有する。
【図面の簡単な説明】
図１は、電解工程の概要を示す図である。TECHNICAL FIELD The present invention relates to a method for producing high-purity nickel having a purity of 5 N (99.999 wt%) or more by electrolytic refining using a nickel-containing solution, high-purity nickel, a sputtering target composed of the high-purity nickel, and the sputtering target. It relates to the formed thin film.
BACKGROUND ART In general, high-purity nickel is required to reduce alkali metals, radioactive elements, transition metal elements, and gas components as much as possible, and particularly for forming VLSI electrodes and wiring, or forming magnetic thin films, Widely used as a sputtering target material.
Alkali metals such as Na and K easily move in the gate insulating film and cause deterioration of MOS-LSI interface characteristics. Radioactive elements such as U and Th cause soft errors in the device due to emitted α-rays. On the other hand, transition metal elements such as Fe also cause troubles at the interface junction.
Further, gas components such as carbon and oxygen are not preferred because they also cause particles to be generated during sputtering.
In general, when producing high-purity nickel at the 5N level, it is common to purify the solution by ion exchange or solvent extraction and then further purify the solution by electrowinning or electrolytic refining. The method of employing a complicated solvent extraction step is inefficient because the steps are complicated and the safety of the extractant must be taken into consideration because a special solvent is required.
In the case of producing high-purity nickel of the 5N level, it is considered to be a relatively simple method to produce nickel by using a nickel-containing solution by electrolysis. It was not a target.
DISCLOSURE OF THE INVENTION The present invention provides a simple method for electrolyzing a nickel raw material containing a large amount of iron, carbon, oxygen and the like using a nickel-containing solution, and has a purity of 5N (99.999 wt%) from the raw material. The purpose of the present invention is to provide a technique for efficiently producing the above high-purity nickel.
In order to solve the above problems, the knowledge that impurities such as iron are removed from the anolyte of the nickel-containing solution as hydroxide and the liquid after the removal is used as catholyte can efficiently produce high-purity nickel. Obtained.
Based on this finding, the present invention provides: When electrolysis is performed using a nickel-containing solution as an electrolytic solution, the anolyte is adjusted to pH 2 to 5, and impurities such as iron, cobalt, and copper contained in the anolyte are added to an oxidizing agent to convert the impurities to hydroxide. The impurities are removed by a combination of one or more of the following methods: removing the impurities by precipitation, removing the impurities by preliminary electrolysis, and removing the impurities by a substitution reaction with a Ni foil. After that, impurities are further removed using a filter, and the solution after the removal is used as catholyte to perform electrolysis. The anode and cathode are separated by a diaphragm, the anolyte is extracted intermittently or continuously, and an oxidizing agent is added thereto to precipitate impurities such as iron as hydroxide, and then the impurities are removed using a filter. 2. The method for producing high-purity nickel as described in 1 above, wherein the liquid after the removal is intermittently or continuously supplied to the cathode side. The anode and cathode are separated by a diaphragm, the anolyte is extracted intermittently or continuously, and this anolyte is pre-electrolyzed to remove impurities such as iron, cobalt, and copper, and then further removed using a filter to remove impurities. 2. The method for producing high-purity nickel according to the first aspect, wherein the subsequent solution is intermittently or continuously supplied to the cathode side.
4. The anode and the cathode are separated by a diaphragm, the anolyte is extracted intermittently or continuously, and nickel foil is put into the anolyte to remove impurities such as iron, cobalt, and copper by a substitution reaction. 2. The method for producing high-purity nickel as described in 1 above, wherein the solution is removed intermittently or continuously on the cathode side.
5. 5. The method for producing high-purity nickel according to any one of 1 to 4 above, wherein activated carbon is used as a filter. 6. The method for producing high-purity nickel according to any one of 1 to 5 above, wherein the concentration of iron in the electrolyte after passing through the filter is 1 mg / L or less. 7. The method for producing high-purity nickel according to any one of 1 to 6 above, wherein the electrodeposited nickel obtained by the electrolysis is subjected to vacuum melting such as electron beam melting. High-purity nickel, characterized by being 5N (99.999 wt%) or more excluding gas components, O: 30 wtppm or less as impurities, and C, N, S, P and F being 10 wtppm or less, respectively. And a thin film formed by sputtering using the target. 5N (99.999 wt%) or more except for the gas components produced by the above 1 to 7; O: 30 wtppm or less as impurities; and C, N, S, P, and F each being 10 wtppm or less. An object of the present invention is to provide a high purity nickel, a target made of the high purity nickel, and a thin film formed by sputtering using the target.
BEST MODE FOR CARRYING OUT THE INVENTION Using an electrolytic cell 1 shown in FIG. 1, a 4N-level massive nickel raw material 2 is put into an anode basket 3 to form an anode 5, and electrolysis is performed using nickel or the like for a cathode 4. The nickel raw material mainly contains a large amount of iron, carbon, oxygen and the like.
The electrolysis is performed at a bath temperature of 10 to 70 ° C., a nickel concentration of 20 to 120 g / L, and a current density of 0.1 to 10 A / dm 2 . If the current density is less than 0.1 A / dm 2 , the productivity is poor. If the current density exceeds 10 A / dm 2 , nodules are generated and the anode 5 and the cathode 4 come into contact with each other. The range is 10 A / dm 2 .
The anode 5 and the cathode 4 are separated by a diaphragm 6, and the anolyte is intermittently or continuously extracted. Anolyte is adjusted to pH 2-5. The cathode box is separated from the outer liquid (anolyte) via a diaphragm. An oxidizing agent 7 is added to the extracted anolyte to precipitate impurities such as iron, cobalt and copper as hydroxide. That is, divalent iron becomes trivalent by the oxidizing agent 7 and precipitates as Fe (OH) 3 . As the oxidizing agent 7, hydrogen peroxide, nitric acid or the like can be used.
Further, the extracted anolyte can be put in a preliminary electrolytic cell, and impurities such as iron, cobalt, and copper can be removed by electrolysis.
Furthermore, the extracted anolyte is placed in a replacement tank, and the impurities such as iron, cobalt, and copper in the electrolytic solution are replaced with nickel foil to remove these impurities.
Although FIG. 1 shows a step of adding an oxidizing agent, the step 7 can be easily removed by replacing the step 7 with a preliminary electrolysis or replacement method.
The impurities can also be removed by combining each of the above-mentioned oxidizing agents, pre-electrolysis or substitution methods.
The impurities such as the precipitate are removed using the filter 8. Activated carbon should be used for the filter. The activated carbon filter 8 has an effect of removing organic substances eluted from a container or the like, in addition to the impurities such as the precipitated oxide. As described above, the concentration of iron in the electrolyte can be reduced to 1 mg / L or less.
After removing the impurities, this solution is intermittently or continuously introduced into the cathode side, and electrolytically purified using as a catholyte.
The current efficiency is 80-100%. Thus, electrodeposited nickel having a purity of 5N (precipitated on the cathode) is obtained. That is, it is 5N (99.999 wt%) or more, excluding gas components, O: 30 wtppm or less as impurities, and C, N, S, P, F, and H can each be 10 wtppm or less.
Further, the electrodeposited nickel obtained by electrolysis can be subjected to vacuum melting such as electron beam melting. By this vacuum melting, alkali metals such as Na and K and other volatile impurities and gas components can be effectively removed.
Further, in the present invention, since no ion-exchange resin or solvent extraction is performed, no organic matter is mixed, and impurity elements due to the organic solvent can be suppressed.
Examples and Comparative Examples Next, examples of the present invention will be described. This embodiment is merely an example, and the present invention is not limited to this example. That is, within the scope of the technical idea of the present invention, all aspects or modifications other than the examples are included.
(Example 1)
Using an electrolytic cell as shown in FIG. 1, electrolysis was carried out using 1 kg of a 4N-level massive nickel raw material as an anode and a 2N-level nickel plate as a cathode. Table 1 shows the impurity contents of the raw materials. The nickel raw material mainly contains a large amount of iron, carbon, oxygen and the like.
At a bath temperature of 50 ° C., 1 mol / L of hydrofluoric acid was added with a sulfuric acid-based electrolyte, nickel concentration was 50 g / L, current density was 2 A / dm 2 , and electrolysis time was 40 hours.
The pH of the solution was adjusted to 2. At this time, the anolyte is extracted intermittently. Hydrogen peroxide (H 2 O 2 ) was added to the extracted anolyte to convert divalent iron to trivalent, and impurities such as iron were precipitated as hydroxide Fe (OH) 3 .
Further, impurities such as precipitates were removed using an activated carbon filter. As described above, the concentration of iron in the electrolytic solution could be reduced to 1 mg / L or less.
After removing the impurities, this solution was intermittently introduced into the cathode side, that is, into the anode basket, and electrolyzed using as a catholyte.
About 1 kg of electrodeposited nickel (deposited on the cathode) was obtained. Purity achieved 5N. That is, it was 5 N (99.999 wt%) or more, excluding gas components, O: 30 wt ppm or less as impurities, and C, N, S, P, and F were each 10 wt ppm or less. The above results are shown in Table 1 in comparison with the raw materials.
Figure 2003014421
(Example 2)
Using the same electrolytic cell as in Example 1, electrolysis was performed using a 4N-level massive raw material nickel as an anode and a 3N-level nickel plate as a cathode.
The bath temperature was 30 ° C., the concentration of nickel was 80 g / L, the current density was 5 A / dm 2 , and the electrolysis time was 40 hours with a hydrochloric acid-based electrolyte.
The pH of the solution was adjusted to 2 as in Example 1. At this time, the anolyte is extracted intermittently. Hydrogen peroxide (H 2 O 2 ) was added to the extracted anolyte to convert divalent iron to trivalent, and impurities such as iron were precipitated as hydroxide Fe (OH) 3 .
Further, impurities such as precipitates were removed using an activated carbon filter. As described above, the concentration of iron in the electrolytic solution could be reduced to 1 mg / L or less.
After removing the impurities, this solution was intermittently introduced into the cathode side, that is, into the anode basket, and electrolyzed using as a catholyte.
About 1 kg of electrodeposited nickel (deposited on the cathode) was obtained. The deposited nickel was further subjected to electron beam melting. Electron beam melting conditions were 1A, 30 kW, and a degree of vacuum of 2 to 5 × 10 −4 mmHg. The above results are also shown in Table 1.
(Comparative Example 1)
Using an electrolytic cell as shown in FIG. 1, electrolysis was performed using 1 kg of a 4N-level massive nickel raw material as an anode and a 3N-level nickel plate as a cathode. Table 1 shows the impurity contents of the raw materials.
At a bath temperature of 50 ° C., 1 mol / L of hydrofluoric acid was added with a sulfuric acid-based electrolyte, nickel concentration was 50 g / L, current density was 2 A / dm 2 , and electrolysis time was 40 hours.
The pH of the solution was adjusted to 2. At this time, electrolysis was continued without extracting the anolyte.
About 1 kg of electrodeposited nickel (deposited on the cathode) was obtained.
The above results are also shown in Table 1.
As shown in Table 1, in Example 1, 50 wtppm of iron as a raw material can be reduced to 2 wtppm, oxygen of 200 wtppm can be reduced to 20 wtppm, carbon of 50 wtppm can be reduced to less than 10 wtppm, and C, N, S, P and F can be reduced to 10 wtppm. Was.
Further, in Example 2, it was possible to reduce the content to 1 wtppm of iron, less than 10 wtppm of oxygen, and less than 10 wtppm of other impurities.
On the other hand, in Comparative Example 1, C, N, S, P, and F at 10 wtppm could each be less than 10 wtppm. Was difficult.
(Example 3)
Electrolysis was performed using 1 kg of a 3N-level massive nickel raw material as an anode and a 2N-level aluminum plate as a cathode. Table 2 shows the impurity contents of the raw materials. This nickel raw material contains a large amount of iron, cobalt, copper, carbon, oxygen and the like.
The electrolysis conditions were as follows: a bath temperature of 40 ° C., 1 mol / L of hydrochloric acid added to a sulfuric acid-based electrolyte, a nickel concentration of 100 g / L, a current density of 3 A / dm 2 , and an electrolysis time of 25 hours.
The pH of the solution was adjusted to 2.5. At this time, the anolyte is extracted intermittently. The extracted anolyte was subjected to electrolysis at a current density of 0.1 A / dm 2 in a preliminary electrolytic cell to remove iron, cobalt, copper, and the like.
Further, an organic substance in the electrolytic solution was removed using an activated carbon filter. As described above, the concentration of iron, cobalt, copper, and the like in the electrolytic solution could be reduced to 1 mg / L or less.
After removing the impurities, this solution was intermittently introduced into the cathode side, that is, into the anode basket, and electrolyzed using as a catholyte.
As a result, about 1.1 kg of electrodeposited nickel was obtained. Purity achieved 5N. That is, it was 5 N or more except for gas components, O: 20 wtppm as impurities, and C, N, S, P, and F were each 10 wtppm or less. The above results are shown in Table 2 in comparison with the raw materials.
(Example 4)
Electrolysis was performed using 1 kg of a 3N-level massive nickel raw material as an anode and a 2N-level titanium plate as a cathode. Table 2 shows the impurity contents of the raw materials. This nickel raw material contains a large amount of iron, cobalt, copper, carbon, oxygen and the like.
The electrolysis conditions were as follows: a bath temperature of 60 ° C., 1 mol / L of hydrochloric acid added to a sulfuric acid-based electrolyte, a nickel concentration of 100 g / L, a current density of 1.5 A / dm 2 , and an electrolysis time of 50 hours.
The pH of the solution was adjusted to 2.7. At this time, the anolyte is extracted intermittently. The extracted anolyte was replaced with impurities in the electrolytic solution using a 2N-level Ni foil in a replacement tank to remove iron, cobalt, copper, and the like.
Further, an organic substance in the electrolytic solution was removed using an activated carbon filter. As described above, the concentration of iron, cobalt, copper, and the like in the electrolytic solution could be reduced to 1 mg / L or less.
After removing the impurities, this solution was intermittently introduced into the cathode side, that is, into the anode basket, and electrolyzed using as a catholyte.
As a result, about 1.1 kg of electrodeposited nickel was obtained. Purity achieved 5N. That is, it was 5N or more except for gas components, O: 20 wtppm as impurities, and C, N, S, P, and F could each be 10 wtppm or less. The above results are shown in Table 2 in comparison with the raw materials.
(Example 5)
In the process of Example 3, the anolyte was extracted intermittently, and the extracted anolyte was electrolyzed in a preliminary electrolytic cell at a current density of 0.1 A / dm 2 , which was further subjected to the same substitution reaction as in the substitution tank of Example 4. Under the conditions described above, impurities such as iron, cobalt, and copper were removed (combination of preliminary electrolysis and substitution reaction).
Except for this step, about 1.1 kg of electrodeposited nickel was obtained by the same steps as in Example 3. As a result, the purity was 5 N or more excluding gas components, and O: 10 wt ppm as impurities and C, N, S, P, and F could each be 10 wt ppm or less. The above results are shown in Table 2 in comparison with the raw materials.
Figure 2003014421
From the above, according to the present invention, the anode and the cathode are separated by a diaphragm, the anolyte is extracted intermittently or continuously, and an oxidizing agent is added thereto to precipitate impurities such as iron as hydroxide, and further use a filter. To remove impurities, and to intermittently or continuously put the liquid after the removal on the cathode side and perform electrolysis, it is a simple and extremely convenient method for effectively removing iron and obtaining high-purity nickel. It turns out to be effective.
Effect of the Invention As described above, a nickel-containing solution is used as an electrolytic solution, and iron, carbon, a nickel raw material containing a large amount of oxygen, etc., and a simple method for electrolytic purification using a nickel-containing solution is provided. There is a remarkable effect that high-purity nickel having a purity of 5N (99.999 wt%) or more can be efficiently produced from the same raw material by improving the simple production process.
[Brief description of the drawings]
FIG. 1 is a diagram showing an outline of the electrolysis step.

【０００３】
をカソード側に間歇的又は連続的に入れることを特徴とする上記１記載の高純度ニッケルの製造方法
３．アノードとカソードを隔膜で仕切り、アノライトを間歇的又は連続的に抜き出し、このアノライトを予備電解して鉄、コバルト、銅等の不純物を除去した後、さらにフィルターを使用して不純物を除去し、除去後の液をカソード側に間歇的又は連続的に入れることを特徴とする上記第１記載の高純度ニッケルの製造方法。
４．アノードとカソードを隔膜で仕切り、アノライトを間歇的又は連続的に抜き出し、このアノライトにニッケル箔を入れて置換反応により、鉄、コバルト、銅等の不純物を除去した後、さらにフィルターを使用して不純物を除去し、除去後の液をカソード側に間歇的又は連続的に入れることを特徴とする上記１記載の高純度ニッケルの製造方法。
５．フィルターとして活性炭を使用することを特徴とする上記１〜４のそれぞれに記載の高純度ニッケルの製造方法
６．フィルター通過後の、電解液中の鉄の濃度が１ｍｇ／Ｌ以下であることを特徴とする上記１〜５のそれぞれに記載の高純度ニッケルの製造方法
７．電解によって得られた電析ニッケルを電子ビーム溶解等の真空溶解を行うことを特徴とする上記１〜６のそれぞれに記載の高純度ニッケルの製造方法
８．削除
９．上記１〜７により製造したガス成分を除き５Ｎ（９９．９９９ｗｔ％）以上であり、不純物としてＯ：３０ｗｔｐｐｍ以下、Ｃ，Ｎ，Ｓ，[0003]
2. The method for producing high-purity nickel according to 1 above, wherein the high-purity nickel is intermittently or continuously put on the cathode side. The anode and cathode are separated by a diaphragm, the anolyte is extracted intermittently or continuously, and this anolyte is pre-electrolyzed to remove impurities such as iron, cobalt, and copper, and then further removed using a filter to remove impurities. 2. The method for producing high-purity nickel according to the first aspect, wherein the subsequent solution is intermittently or continuously supplied to the cathode side.
4. The anode and the cathode are separated by a diaphragm, the anolyte is extracted intermittently or continuously, and nickel foil is put into the anolyte to remove impurities such as iron, cobalt, and copper by a substitution reaction. 2. The method for producing high-purity nickel as described in 1 above, wherein the solution is removed intermittently or continuously on the cathode side.
5. 5. The method for producing high-purity nickel according to any one of 1 to 4 above, wherein activated carbon is used as a filter. 6. The method for producing high-purity nickel according to any one of 1 to 5 above, wherein the concentration of iron in the electrolyte after passing through the filter is 1 mg / L or less. 7. The method for producing high-purity nickel according to any one of 1 to 6 above, wherein the electrodeposited nickel obtained by the electrolysis is subjected to vacuum melting such as electron beam melting. Delete 9. Except for the gas components produced by the above 1 to 7, the content is 5 N (99.999 wt%) or more, and O: 30 wt ppm or less as impurities, C, N, S,

【０００６】
実施例及び比較例
次に、本発明の実施例について説明する。なお、本実施例はあくまで一例であり、この例に制限されるものではない。すなわち、本発明の技術思想の範囲内で、実施例以外の態様あるいは変形を全て包含するものである。
（実施例１）
図１に示すような電解槽を用い、４Ｎレベルの塊状のニッケル原料１ｋｇをアノードとし、カソードに２Ｎレベルのニッケル板を使用して電解を行った。原料の不純物の含有量を表１に示す。ニッケル原料には、主として鉄、炭素、酸素等が多く含有されている。
浴温５０°Ｃ、硫酸系電解液で弗酸を１ｍｏｌ／Ｌを添加し、ニッケル濃度５０ｇ／Ｌ、電流密度２Ａ／ｄｍ２、電解時間４０ｈｒ実施した。
液のｐＨを２に調節した。この時、アノライトを間歇的に抜き出す。抜き出したアノライトに過酸化水素（Ｈ２Ｏ２）を入れて、２価の鉄を３価に変え、鉄等の不純物を水酸化物Ｆｅ（ＯＨ）３として沈殿させた。
さらに、この沈殿物等の不純物を、活性炭フィルターを使用して除去した。以上によって、電解液中の鉄の濃度が１ｍｇ／Ｌ以下とすることができた。
不純物の除去後、この液をカソード側すなわちカソードバスケット内に間歇的に導入し、カソライトとして使用して電解した。
電析ニッケル（カソードに析出）約１ｋｇを得た。純度は５Ｎを達成した。すなわち、ガス成分を除き５Ｎ（９９．９９９ｗｔ％）以上であり、不純物としてＯ：３０ｗｔｐｐｍ以下、Ｃ，Ｎ，Ｓ，Ｐ，Ｆがそれぞれ１０ｗｔｐｐｍ以下とすることができた。以上の結果を原料と対比して、表１に示す。[0006]
Examples and Comparative Examples Next, examples of the present invention will be described. This embodiment is merely an example, and the present invention is not limited to this example. That is, within the scope of the technical idea of the present invention, all aspects or modifications other than the examples are included.
(Example 1)
Using an electrolytic cell as shown in FIG. 1, electrolysis was carried out using 1 kg of a 4N-level massive nickel raw material as an anode and a 2N-level nickel plate as a cathode. Table 1 shows the impurity contents of the raw materials. The nickel raw material mainly contains a large amount of iron, carbon, oxygen and the like.
At a bath temperature of 50 ° C., 1 mol / L of hydrofluoric acid was added with a sulfuric acid-based electrolyte, nickel concentration was 50 g / L, current density was 2 A / dm 2 , and electrolysis time was 40 hours.
The pH of the solution was adjusted to 2. At this time, the anolyte is extracted intermittently. Hydrogen peroxide (H 2 O 2 ) was added to the extracted anolyte to convert divalent iron to trivalent, and impurities such as iron were precipitated as hydroxide Fe (OH) 3 .
Further, impurities such as precipitates were removed using an activated carbon filter. As described above, the concentration of iron in the electrolytic solution could be reduced to 1 mg / L or less.
After removal of the impurities, this solution was intermittently introduced into the cathode side, that is, into the cathode basket, and used as catholyte for electrolysis.
About 1 kg of electrodeposited nickel (deposited on the cathode) was obtained. Purity achieved 5N. That is, it was 5 N (99.999 wt%) or more, excluding gas components, O: 30 wt ppm or less as impurities, and C, N, S, P, and F were each 10 wt ppm or less. The above results are shown in Table 1 in comparison with the raw materials.

【０００８】
不純物の除去後、この液をカソード側すなわちカソードバスケット内に間歇的に導入し、カソライトとして使用して電解した。
電析ニッケル（カソードに析出）約１ｋｇを得た。この電析ニッケルをさらに電子ビーム溶解した。電子ビーム溶解条件は、１Ａ、３０ｋＷ、真空度２〜５×１０−４ｍｍＨｇで実施した。以上の結果を、同様に表１に示す。
（比較例１）
図１に示すような電解槽を用い、４Ｎレベルの塊状のニッケル原料１ｋｇをアノードとし、カソードに３Ｎレベルのニッケル板を使用して電解を行った。原料の不純物の含有量を表１に示す。
浴温５０°Ｃ、硫酸系電解液で弗酸を１ｍｏｌ／Ｌを添加し、ニッケル濃度５０ｇ／Ｌ、電流密度２Ａ／ｄｍ２、電解時間４０ｈｒ実施した。
液のｐＨを２は調節した。この時、アノライトを抜き出さず、そのまま電解を続けた。
電析ニッケル（カソードに析出）約１ｋｇを得た。
以上の結果を、同様に表１に示す。
表１に示すように、実施例１では、原料の鉄５０ｗｔｐｐｍが２ｗｔｐｐｍに、酸素２００ｗｔｐｐｍが２０ｗｔｐｐｍに、炭素５０ｗｔｐｐｍが１０ｗｔｐｐｍ未満、Ｃ，Ｎ，Ｓ，Ｐ，Ｆ１０ｗｔｐｐｍをそれぞれ１０ｗｔｐｐｍ未満とすることができた。
また、実施例２では、鉄１ｗｔｐｐｍ、酸素１０ｗｔｐｐｍ未満、その他の不純物１０ｗｔｐｐｍ未満とすることができた。
これに対し、比較例１では、Ｃ，Ｎ，Ｓ，Ｐ，Ｆ１０ｗｔｐｐｍをそれぞれ１０ｗｔｐｐｍ未満とすることができたが、鉄５０ｗｔｐｐｍ、また酸素６０ｗｔｐｐｍで実施例に比べ精製効果が劣り、特に鉄の除去が困難であった。[0008]
After removal of the impurities, this solution was intermittently introduced into the cathode side, that is, into the cathode basket, and used as catholyte for electrolysis.
About 1 kg of electrodeposited nickel (deposited on the cathode) was obtained. The deposited nickel was further subjected to electron beam melting. Electron beam melting conditions were implemented at 1 A, 30 kW, and a degree of vacuum of 2 to 5 × 10 −4 mmHg. The above results are also shown in Table 1.
(Comparative Example 1)
Using an electrolytic cell as shown in FIG. 1, electrolysis was performed using 1 kg of a 4N-level massive nickel raw material as an anode and a 3N-level nickel plate as a cathode. Table 1 shows the impurity contents of the raw materials.
At a bath temperature of 50 ° C., 1 mol / L of hydrofluoric acid was added with a sulfuric acid-based electrolyte, nickel concentration was 50 g / L, current density was 2 A / dm 2 , and electrolysis time was 40 hours.
The pH of the solution was adjusted to 2. At this time, electrolysis was continued without extracting the anolyte.
About 1 kg of electrodeposited nickel (deposited on the cathode) was obtained.
The above results are also shown in Table 1.
As shown in Table 1, in Example 1, 50 wtppm of iron as a raw material can be reduced to 2 wtppm, oxygen of 200 wtppm can be reduced to 20 wtppm, carbon of 50 wtppm can be reduced to less than 10 wtppm, and C, N, S, P and F can be reduced to 10 wtppm. Was.
Further, in Example 2, it was possible to reduce the content to 1 wtppm of iron, less than 10 wtppm of oxygen, and less than 10 wtppm of other impurities.
On the other hand, in Comparative Example 1, C, N, S, P, and F were each 10 wtppm less than 10 wtppm. However, iron was 50 wtppm and oxygen was 60 wtppm, and the purification effect was inferior to that of the embodiment. Was difficult.

【０００９】
（実施例３）
３Ｎレベルの塊状のニッケル原料１ｋｇをアノードとし、カソードに２Ｎレベルのアルミニウム板を使用して電解を行った。原料の不純物の含有量を表２に示す。このニッケル原料には、鉄、コバルト、銅、炭素、酸素等が多く含有されている。
電解条件は、浴温４０°Ｃ、硫酸系電解液に塩酸を１ｍｏｌ／Ｌを添加し、ニッケル濃度１００ｇ／Ｌ、電流密度３Ａ／ｄｍ２、電解時間２５ｈｒ実施した。
液のｐＨは２．５に調節した。この時、アノライトを間歇的に抜き出す。抜き出したアノライトは、予備電解槽で電流密度０．１Ａ／ｄｍ２で電解を行い、鉄、コバルト、銅等を除去した。
さらに、活性炭フィルターを使用して電解液中の有機物を除去した。以上によって、電解液中の鉄、コバルト、銅等の濃度を１ｍｇ／Ｌ以下にすることができた。
不純物の除去後、この液をカソード側すなわちカソードバスケット内に間歇的に導入し、カソライトとして使用して電解した。
その結果、電析ニッケル約１．１ｋｇを得た。純度は５Ｎを達成した。すなわち、ガス成分を除き５Ｎ以上であり、不純物としてＯ：２０ｗｔｐｐｍ、Ｃ，Ｎ，Ｓ，Ｐ，Ｆはそれぞれ１０ｗｔｐｐｍ以下とすることができた。以上の結果を原料と対比して、表２に示す。
（実施例４）
３Ｎレベルの塊状のニッケル原料１ｋｇをアノードとし、カソードに２Ｎレベルのチタン板を使用して電解を行った。原料の不純物の含有量を表２に示す。このニッケル原料には、鉄、コバルト、銅、炭素、酸素等が多く含有されている。[0009]
(Example 3)
Electrolysis was performed using 1 kg of a 3N-level massive nickel raw material as an anode and a 2N-level aluminum plate as a cathode. Table 2 shows the impurity contents of the raw materials. This nickel raw material contains a large amount of iron, cobalt, copper, carbon, oxygen and the like.
The electrolysis conditions were as follows: a bath temperature of 40 ° C., 1 mol / L of hydrochloric acid added to a sulfuric acid-based electrolyte, a nickel concentration of 100 g / L, a current density of 3 A / dm 2 , and an electrolysis time of 25 hours.
The pH of the solution was adjusted to 2.5. At this time, the anolyte is extracted intermittently. The extracted anolyte was subjected to electrolysis at a current density of 0.1 A / dm 2 in a preliminary electrolytic cell to remove iron, cobalt, copper, and the like.
Further, an organic substance in the electrolytic solution was removed using an activated carbon filter. As described above, the concentration of iron, cobalt, copper, and the like in the electrolytic solution could be reduced to 1 mg / L or less.
After removal of the impurities, this solution was intermittently introduced into the cathode side, that is, into the cathode basket, and used as catholyte for electrolysis.
As a result, about 1.1 kg of electrodeposited nickel was obtained. Purity achieved 5N. That is, it was 5N or more except for gas components, O: 20 wtppm as impurities, and C, N, S, P, and F could each be 10 wtppm or less. The above results are shown in Table 2 in comparison with the raw materials.
(Example 4)
Electrolysis was performed using 1 kg of a 3N-level massive nickel raw material as an anode and a 2N-level titanium plate as a cathode. Table 2 shows the impurity contents of the raw materials. This nickel raw material contains a large amount of iron, cobalt, copper, carbon, oxygen and the like.

【００１０】
電解条件は、浴温６０°Ｃ、硫酸系電解液に塩酸を１ｍｏｌ／Ｌを添加し、ニッケル濃度１００ｇ／Ｌ、電流密度１．５Ａ／ｄｍ２、電解時間５０ｈｒ実施した。
液のｐＨは２．７に調節した。この時、アノライトを間歇的に抜き出す。抜き出したアノライトは、置換槽で２ＮレベルのＮｉ箔で電解液中の不純物との置換を行い、鉄、コバルト、銅等を除去した。
さらに、活性炭フィルターを使用して電解液中の有機物を除去した。以上によって、電解液中の鉄、コバルト、銅等の濃度を１ｍｇ／Ｌ以下にすることができた。
不純物の除去後、この液をカソード側すなわちカソードバスケット内に間歇的に導入し、カソライトとして使用して電解した。
その結果、電析ニッケル約１．１ｋｇを得た。純度は５Ｎを達成した。すなわち、ガス成分を除き５Ｎ以上であり、不純物としてＯ：２０ｗｔｐｐｍ、Ｃ，Ｎ，Ｓ，Ｐ，Ｆはそれぞれ１０ｗｔｐｐｍ以下とすることができた。以上の結果を原料と対比して、同様に表２に示す。
（実施例５）
上記実施例３の工程において、アノライトを間歇的に抜き出し、抜き出したアノライトを予備電解槽で電流密度０．１Ａ／ｄｍ２で電解を行い、これをさらに実施例４の置換槽における置換反応と同一の条件で鉄、コバルト、銅等の不純物を除去した（予備電解と置換反応の組合せ）。
そして、この工程以外は実施例３と同一の工程により電析ニッケル約１．１ｋｇを得た。この結果、純度はガス成分を除き５Ｎ以上であり、不純物としてＯ：１０ｗｔｐｐｍ、Ｃ，Ｎ，Ｓ，Ｐ，Ｆはそれぞれ１０ｗｔｐｐｍ以下とすることができた。以上の結果を原料と対比して、同様に表２に示す。[0010]
The electrolysis conditions were as follows: a bath temperature of 60 ° C., 1 mol / L of hydrochloric acid added to a sulfuric acid-based electrolyte, a nickel concentration of 100 g / L, a current density of 1.5 A / dm 2 , and an electrolysis time of 50 hours.
The pH of the solution was adjusted to 2.7. At this time, the anolyte is extracted intermittently. The extracted anolyte was replaced with impurities in the electrolytic solution using a 2N-level Ni foil in a replacement tank to remove iron, cobalt, copper, and the like.
Further, an organic substance in the electrolytic solution was removed using an activated carbon filter. As described above, the concentration of iron, cobalt, copper, and the like in the electrolytic solution could be reduced to 1 mg / L or less.
After removal of the impurities, this solution was intermittently introduced into the cathode side, that is, into the cathode basket, and used as catholyte for electrolysis.
As a result, about 1.1 kg of electrodeposited nickel was obtained. Purity achieved 5N. That is, it was 5N or more except for gas components, O: 20 wtppm as impurities, and C, N, S, P, and F could each be 10 wtppm or less. The above results are shown in Table 2 in comparison with the raw materials.
(Example 5)
In the process of Example 3, the anolyte was extracted intermittently, and the extracted anolyte was electrolyzed in a preliminary electrolyzer at a current density of 0.1 A / dm 2. Under the conditions described above, impurities such as iron, cobalt, and copper were removed (combination of preliminary electrolysis and substitution reaction).
Except for this step, about 1.1 kg of electrodeposited nickel was obtained by the same steps as in Example 3. As a result, the purity was 5 N or more excluding gas components, and O: 10 wt ppm as impurities and C, N, S, P, and F could each be 10 wt ppm or less. The above results are shown in Table 2 in comparison with the raw materials.

Claims (9)

電解液としてニッケル含有溶液を用いて電解する際に、アノライトをｐＨ２〜５に調整し、アノライトに含有されている鉄、コバルト、銅等の不純物を、酸化剤を入れて該不純物を水酸化物として沈殿除去するか、若しくは予備電解により該不純物を除去するか、又はＮｉ箔を入れて置換反応により該不純物を除去するかの、いずれか１又は２以上の方法を組合せることにより不純物を除去した後、さらにフィルターを使用して不純物を除去し、除去後の液をカソライトとして使用し電解することを特徴とする高純度ニッケルの製造方法。When electrolysis is performed using a nickel-containing solution as an electrolytic solution, the anolyte is adjusted to pH 2 to 5, and impurities such as iron, cobalt, and copper contained in the anolyte are added with an oxidizing agent to convert the impurities to hydroxide. The impurities are removed by a combination of one or more of the following methods: removing the impurities by precipitation, removing the impurities by preliminary electrolysis, or removing the impurities by a substitution reaction with a Ni foil. A method for producing high-purity nickel, further comprising removing impurities using a filter, and using the removed solution as catholyte for electrolysis. アノードとカソードを隔膜で仕切り、アノライトを間歇的又は連続的に抜き出し、これに酸化剤を入れて鉄等の不純物を水酸化物として沈殿させ、さらにフィルターを使用して不純物を除去し、除去後の液をカソード側に間歇的又は連続的に入れることを特徴とする請求の範囲第１項記載の高純度ニッケルの製造方法。The anode and cathode are separated by a diaphragm, the anolyte is extracted intermittently or continuously, an oxidizing agent is added to the precipitate to precipitate impurities such as iron as hydroxide, and then the impurities are removed using a filter. 2. The method for producing high-purity nickel according to claim 1, wherein said solution is intermittently or continuously supplied to the cathode side. アノードとカソードを隔膜で仕切り、アノライトを間歇的又は連続的に抜き出し、このアノライトを予備電解して鉄、コバルト、銅等の不純物を除去した後、さらにフィルターを使用して不純物を除去し、除去後の液をカソード側に間歇的又は連続的に入れることを特徴とする請求の範囲第１項記載の高純度ニッケルの製造方法。The anode and cathode are separated by a diaphragm, the anolyte is extracted intermittently or continuously, and this anolyte is pre-electrolyzed to remove impurities such as iron, cobalt, and copper, and then further removed using a filter to remove impurities. 2. The method for producing high-purity nickel according to claim 1, wherein the subsequent liquid is intermittently or continuously supplied to the cathode side. アノードとカソードを隔膜で仕切り、アノライトを間歇的又は連続的に抜き出し、このアノライトにニッケル箔を入れて置換反応により、鉄、コバルト、銅等の不純物を除去した後、さらにフィルターを使用して不純物を除去し、除去後の液をカソード側に間歇的又は連続的に入れることを特徴とする請求の範囲第１項記載の高純度ニッケルの製造方法。The anode and the cathode are separated by a diaphragm, the anolyte is extracted intermittently or continuously, and nickel foil is put into the anolyte to remove impurities such as iron, cobalt, and copper by a substitution reaction. 2. The method for producing high-purity nickel according to claim 1, wherein the solution after the removal is removed intermittently or continuously on the cathode side. フィルターとして活性炭を使用することを特徴とする請求の範囲第１項〜第４項のそれぞれに記載の高純度ニッケルの製造方法。The method for producing high-purity nickel according to any one of claims 1 to 4, wherein activated carbon is used as a filter. フィルター通過後の、電解液中の鉄の濃度が１ｍｇ／Ｌ以下であることを特徴とする請求の範囲第１項〜第５項のそれぞれに記載の高純度ニッケルの製造方法。The method for producing high-purity nickel according to any one of claims 1 to 5, wherein the concentration of iron in the electrolyte after passing through the filter is 1 mg / L or less. 電解によって得られた電析ニッケルを電子ビーム溶解等の真空溶解を行うことを特徴とする請求の範囲第１項〜第６項のそれぞれに記載の高純度ニッケルの製造方法。The method for producing high-purity nickel according to any one of claims 1 to 6, wherein the electrodeposited nickel obtained by the electrolysis is subjected to vacuum melting such as electron beam melting. ガス成分を除き５Ｎ（９９．９９９ｗｔ％）以上であり、不純物としてＯ：３０ｗｔｐｐｍ以下、Ｃ，Ｎ，Ｓ，Ｐ，Ｆがそれぞれ１０ｗｔｐｐｍ以下であることを特徴とする高純度ニッケル、同高純度ニッケルからなるターゲット及び同ターゲットを使用してスパッタリングにより形成した薄膜。High-purity nickel, characterized by being 5N (99.999 wt%) or more excluding gas components, O: 30 wtppm or less as impurities, and C, N, S, P and F being 10 wtppm or less, respectively. And a thin film formed by sputtering using the target. 請求の範第１項〜第７項により製造したガス成分を除き５Ｎ（９９．９９９ｗｔ％）以上であり、不純物としてＯ：３０ｗｔｐｐｍ以下、Ｃ，Ｎ，Ｓ，Ｐ，Ｆがそれぞれ１０ｗｔｐｐｍ以下であることを特徴とする高純度ニッケル、同高純度ニッケルからなるターゲット及び同ターゲットを使用してスパッタリングにより形成した薄膜。Except for the gas components produced according to claims 1 to 7, the content is 5 N (99.999 wt%) or more, O: 30 wt ppm or less as impurities, and each of C, N, S, P, and F is 10 wt ppm or less. A high-purity nickel, a target made of the high-purity nickel, and a thin film formed by sputtering using the target.
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